Phosphono paraffins

ABSTRACT

Aspects described herein generally relate to methods of making a phosphono paraffin comprising forming a reaction mixture by mixing a haloparaffin, a phosphite, and sodium iodide. Methods comprise heating the reaction mixture to form the phosphono paraffin. Aspects described herein further relate to a phosphono paraffin represented by formula (I): 
     
       
         
         
             
             
         
       
     
     wherein each instance of R 1  is independently —H 
     
       
         
         
             
             
         
       
     
     wherein each instance of R 2  and R 3  is independently linear or branched C 1-20  alkyl, C 1-20  cycloalkyl, or aryl; the number of instances where R 1  is 
     
       
         
         
             
             
         
       
     
     of formula (I) is between about 2 and about 8; and n is an integer between 4 and 22.

FIELD

Aspects of the present disclosure generally relate to phosphonoparaffins, hydraulic fluids having phosphono paraffins, and methods ofmaking phosphono paraffins.

BACKGROUND

Many vehicles, such as aircraft, cars, trucks, etc., have one or morehydraulic systems which are drives or transmission systems that usepressurized hydraulic fluid to power hydraulic machinery. For example,early vehicles had hydraulic brake systems. As vehicles became moresophisticated, newer systems with hydraulic power were developed.Hydraulic systems in, for example, an aircraft provide for the operationof vehicle components, such as landing gear, flaps, flight controlsurfaces, and brakes.

A hydraulic system has a power generating device (pump) reservoir,accumulator, heat exchanger, and filtering system. System operatingpressure may vary from a couple hundred pounds per square inch (psi) insmall vehicles and rotorcraft to 5,000 psi in large vehicles.

Hydraulic system fluids (“hydraulic fluids”) flow through components ofthe hydraulic system during use to transmit and distribute forces tovarious components of the hydraulic system. If a number of passagesexist in a system, pressure can be distributed through the variouscomponents of the system. Hydraulic operations have only negligible lossdue to fluid friction.

If incompressibility and fluidity were the only qualities required, mostliquids that are not too thick could be used in a hydraulic system.However, other properties should be considered when selecting a desiredhydraulic fluid for a particular hydraulic system.

One of those properties is viscosity, which is a resistance of the fluidto flow. A liquid such as gasoline that has a low viscosity flowseasily, while a liquid such as tar that has a high viscosity flowsslowly. Viscosity increases as temperature decreases. A liquid for agiven hydraulic system should have enough viscosity to give a good sealat pumps, valves, and pistons, but should not be so thick that it offersresistance to flow, leading to power loss and higher operatingtemperatures which may promote wear of hydraulic system components. Afluid that is not viscous enough can wear moving parts or parts thathave heavy loads.

Another property pertinent to hydraulic fluids is the fire point of thefluid, which is the temperature at which a substance gives off vapor insufficient quantity to ignite and continue to burn when exposed to aspark or flame. Like a flash point, a high fire point is desirable ofhydraulic liquids.

Known hydraulic fluids do not possess ideal properties as discussedabove. Polyalphaolefin-based hydraulic fluids are fire-resistant buthave a high viscosity and are limited to use down to −40° F. Phosphateester-based (Skydrol®) hydraulic fluids are not entirely fire-resistantand under certain conditions, they burn. Furthermore,polyalphaolefin-based hydraulic fluids and phosphate ester-basedhydraulic fluids do not mix with each other. Furthermore,fluorocarbon-based hydraulic fluids tend to degrade paint and titaniumcouplings on the hydraulic lines of a hydraulic system. There is also amovement to ban production of chlorocarbon-based and fluorocarbon-basedhydraulic fluids because of their toxicity and poor biodegradability.For example, chloroparaffins are stable in soil and persist in soil foryears, having a half-life (T_(1/2)) of at least months to years.

Furthermore, synthesis of hydraulic fluids tends to be laborious andcost intensive. Conventional reactions, such as the Arbuzov reaction, donot yield hydraulic fluids having ideal properties as described above.An Arbuzov reaction proceeds by reacting a primary alkyl halide with aphosphite to form a primary phosphono-substituted product. The Arbuzovreaction does not proceed readily using primary, secondary, or tertiaryfluoro alkane starting material or using secondary or tertiary chloro-,bromo-, iodo-alkane starting materials.

Therefore, there is a need in the art for new and improved hydraulicfluids and methods of making hydraulic fluids.

SUMMARY

In one aspect, a method of making a phosphono paraffin comprises forminga reaction mixture by mixing a haloparaffin, a phosphite and sodiumiodide. Methods to make the composition comprise heating the reactionmixture to form the phosphono paraffin.

In another aspect, a phosphono paraffin is represented by formula (I):

wherein each instance of R¹ is independently —H or

wherein each instance of R² and R³ is independently linear or branchedC₁₋₂₀ alkyl, C₁₋₂₀ cycloalkyl, or aryl; wherein the number of instanceswhere R¹ is

of formula (I) is between about 2 and about 8; and n is an integerbetween 4 and 22.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toaspects, some of which are illustrated in the appended drawings. It isto be noted, however, that the appended drawings illustrate only typicalaspects of this present disclosure and are therefore not to beconsidered limiting of its scope, for the present disclosure may admitto other equally effective aspects.

FIG. 1 is an ¹H NMR spectrum of Cereclor AS45,

FIG. 2 is an ¹H NMR spectrum of the reaction product of Example 1.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. The figures are not drawn to scale and may be simplifiedfor clarity. It is contemplated that elements and features of one aspectmay be beneficially incorporated in other aspects without furtherrecitation.

DETAILED DESCRIPTION

Aspects of the present disclosure include methods of making phosphonoparaffins. It was discovered that sodium iodide in the presence ofhaloparaffin and phosphite readily promotes phosphono paraffinformation. In at least one aspect, a method of making phosphonoparaffins includes mixing a haloparaffin with a phosphite and sodiumiodide,

Methods of the present disclosure provide access to a new class ofphosphono paraffin compounds. Accordingly, aspects of the presentdisclosure further comprise phosphono paraffins having between about 6and about 24 carbons and between about 2 and about 8 phosphonosubstituents. These compounds can be used as fire-resistant,biodegradable hydraulic fluids. Without being bound by theory, it isbelieved that phosphono paraffins are viable candidates for use asfire-resistant hydraulic fluids because of their long alkyl chains forideal viscosity and phosphonate moieties that meet the desirableparameters for fire-resistance and biodegradability.

Phosphono Paraffins

Phosphono paraffins of the present disclosure have between about 6 andabout 24 carbons and between about 2 and about 8 phosphono substituents.In at least one aspect, a phosphono paraffin has a fire point greaterthan about 200° C., such as greater than about 220° C., such as greaterthan about 240° C. In at least one aspect, a phosphono paraffin has aflash point of greater than about 150° C., such as greater than about170° C., such as greater than about 190° C. In at least one aspect, aphosphono paraffin has a melting point of less than about −40° C., suchas less than about −55° C., such as less than about −70° C.

The flash point and the fire point of a phosphono paraffin can bedetermined by ASTM D92 using a SetaFlash Series 3 Open Cup Flash Pointtester supplied by John Morris Scientific Pty Ltd. The melting point ofa phosphono paraffin can be determined as follows: approximately 1 ml offluid is placed in a 3 mm diameter glass NMR tube, and a stainless steelthermocouple probe inserted into the fluid. The tube is then placed inliquid nitrogen to freeze the fluid, which prevents movement of thethermocouple probe in the frozen fluid. The tube is then slowly warmedand the fluid eventually melts. Upon melting of the fluid, thethermocouple probe can be pulled free. The temperature at which thethermocouple can be pulled from the fluid is taken as the melting point.This process is repeated two more times to obtain an average meltingpoint value.

In at least one aspect, a phosphono paraffin of the present disclosureis represented by formula (I):

wherein each instance of R¹ is independently —H or

wherein each instance of R² and R³ is independently linear or branchedC₁₋₂₀ alkyl, C₁₋₂₀ cycloalkyl, or aryl; the number of instances where R¹is

of formula (I) is between about 2 and about 8; and n is an integerbetween 4 and 22. C₁₋₂₀ alkyl includes C₁₋₁₀ alkyl and C₁₋₅ alkyl. C₁₋₂₀cycloalkyl includes C₁₋₁₀ cycloalkyl and C₁₋₆ cycloalkyl. In at leastone aspect, each instance of R² and R³ is independently linear C₁₋₂₀alkyl. C₁₋₂₀ alkyl includes methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, and decyl. n is an integer between 4 and 22, suchas between about 6 and about 18, such as between about 10 and about 16.In at least one aspect, R² and R³ are the same. In at least one aspect,each of R² and R³ is isopropyl, butyl, or phenyl,

In at least one aspect, a phosphono paraffin comprises:

and combinations thereof; wherein each instance of R¹ and R² isindependently linear or branched C₁₋₂₀ alkyl, C₁₋₂₀ cycloalkyl, or aryl.C₁₋₂₀ alkyl includes C₁₋₁₀ alkyl and C₁₋₅ alkyl. C₁₋₂₀ cycloalkylincludes C₁₋₁₀ cycloalkyl and C₁₋₆ cycloalkyl. In at least one aspect,each instance of R¹ and R² is independently linear C₁₋₂₀ alkyl. C₁₋₂₀alkyl includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosanyl. In at leastone aspect, R¹ and R² are the same. In at least one aspect, each of R¹and R² is isopropyl, butyl, or phenyl.

In at least one aspect, a phosphono paraffin comprises:

and mixtures thereof.

In at least one aspect, a phosphono paraffin includes:

and mixtures thereof.

In at least one aspect, a phosphono paraffin includes:

and mixtures thereof.

In at least one aspect, a phosphono paraffin includes:

and mixtures thereof.

Methods of Making Phosphono Paraffins

It was discovered that synthesizing phosphono paraffins underconventional Arbuzov reaction conditions does not form phosphonoparaffins, It was also discovered that mixing a haloparaffin and aphosphite with sodium idodide promotes phosphono paraffin formation. Inat least one aspect, a method of making a phosphono paraffin comprisesforming a reaction mixture by mixing a haloparaffin with a phosphite andsodium iodide, Haloparaffin includes a chloroparaffin, a bromoparaffin,or an iodoparaffin, A haloparaffin can include one or more secondaryhalogen moieties. The reaction mixture is heated to form a reactionproduct having a phosphono paraffin. The phosphono paraffin may beisolated from the reaction product at an overall yield of between about20% and about 80%, such as between about 40% and about 60%.

As shown in Schemes 1, 2, and 3, a method of making a phosphono paraffinincludes forming a reaction mixture by mixing a haloparaffin (e.g.,chloroparaffin) with a phosphite represented by formula (II):

followed by addition of sodium iodide. R¹ and R² are as described above.R³ is any suitable substituent having an electrophilic atom, such asC₁₋₂₀ alkyl, C₁₋₂₀ cycloalkyl, or aryl. C₁₋₂₀ alkyl includes C₁₋₁₀ alkyland C₁₋₅ alkyl. C₁₋₂₀ cycloalkyl includes C₁₋₁₀ cycloalkyl and C₁₋₆cycloalkyl. In at least one aspect, the phosphite includes triethylphosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite,triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecylphosphite, or mixtures thereof.

The presence of sodium iodide in the reaction mixture promotes formationof the phosphono paraffin. Alternatively, a method of making a phosphonoparaffin comprises forming a reaction mixture by mixing sodium iodidewith a haloparaffin followed by addition of a phosphite. Alternatively,a method of making a phosphono paraffin comprises forming a reactionmixture by mixing sodium iodide with a phosphite followed by addition ofa haloparaffin. As shown in Scheme 1, a reaction mixture can be heatedto promote reaction of at least one of the starting materials to form areaction product having a phosphono paraffin. For example, a reactionmixture can be heated to a temperature of between about 120° C. andabout 200° C., such as between about 130° C. and about 190° C., such asbetween about 140° C. and about 180° C. Furthermore, phosphono paraffinformation is typically exothermic, so the exotherm may be controlled toprevent a runaway reaction at these temperatures. Two non-limitingmethods to control the exotherm include: (1) Arbuzov reactions producealkyl halides as a byproduct, and distilling this byproduct from thereaction mixture removes some heat, and/or (2) phosphite can be cooledand/or added slowly to the reaction mixture to reduce the temperature.

In at least one aspect, a method of making a phosphono paraffincomprises forming a reaction mixture by mixing sodium iodide and ahaloparaffin and heating the reaction mixture and/or stirring thereaction mixture. The reaction mixture is heated to a temperature ofbetween about 120° C. and about 200° C., such as between about 130° C.and about 180° C., such as between about 140° C. and about 160° C. Aftera desired period of time, the reaction mixture can be allowed to coolto, for example, room temperature. A phosphite can be added to thecooled reaction mixture to form a second reaction mixture. The secondreaction mixture can be heated (and/or stirred) to form a reactionproduct. The second reaction mixture can be heated at a temperature ofbetween about 120° C. and about 200° C., such as between about 130° C.and about 180° C., such as between about 140° C. and about 160° C. Thefirst and/or second reaction mixtures can be cooled using any suitablecooling bath to maintain the reaction mixture(s) at a desirabletemperature, such as the temperatures described above. After a desiredperiod of time, the reaction product can be allowed to cool to, forexample, room temperature.

A reaction mixture of the present disclosure can be solvent-free (neat)or can further comprise one or more suitable solvents. Solvents caninclude dimethylsulfoxide, dimethylformamide, chlorobenzene,N-methyl-2-pyrrolidinone, xylenes, and mixtures thereof. A reactionmixture can be stirred.

In one aspect, at least one molar equivalent of phosphite is present ina reaction mixture for every halogen moiety of a haloparaffin startingmaterial. For example, if a haloparaffin has three chlorine moieties,then a molar ratio of phosphite:haloparaffin is at least 3:1. A molarratio of phosphite:haloparaffin is between about 1:1 and about 10:1,such as between about 2:1 and about 6:1, such as between about 3:1 andabout 5:1.

In one aspect, at least one molar equivalent of sodium iodide is presentin a reaction mixture for every halogen moiety of a haloparaffinstarting material. For example, if a haloparaffin has three chlorinemoieties, then a molar ratio of sodium iodide:haloparaffin is at least3:1. A molar ratio of sodium iodide:haloparaffin is between about 1:1and about 10:1, such as between about 2:1 and about 6:1, such as betweenabout 3:1 and about 5:1.

The progress of phosphono paraffin formation during or after methods ofthe present disclosure may be monitored by thin layer chromatographyand/or nuclear magnetic resonance (NMR) spectroscopy.

After heating a reaction mixture of the present disclosure for a desiredperiod of time to form a reaction product, the reaction product isallowed to cool to, for example, room temperature. The phosphonoparaffin of the reaction product can then be isolated from any unreactedhaloparaffin, phosphite and sodium iodide starting materials and asodium halide byproduct, such as sodium chloride. For example, in atleast one aspect, water is added to a reaction product to form abiphasic mixture having an aqueous phase and an organic phase. Thebiphasic mixture may be stirred vigorously or shaken to promote mixingof the two phases. After stirring/shaking, the mixture reforms abiphasic mixture. The aqueous phase comprises sodium iodide and thesodium halide byproduct. The organic phase comprises phosphono paraffinand unreacted haloparaffin (if any) and/or phosphite (if any). Theorganic phase can be drained from the aqueous phase. If the organicphase contains haloparaffin and/or phosphite, the haloparaffin and/orphosphite can be distilled from the phosphono paraffin to yield isolatedphosphono paraffin. Furthermore, some phosphono paraffin may be presentin the aqueous phase after stirring/shaking. Therefore, the aqueousphase may be stirred/shaken with an organic solvent (such as hexane) toform a biphasic mixture after settling, the biphasic mixture having anaqueous phase and an organic (hexane) phase. The organic phase can bedrained from the aqueous phase followed by distillation of hexane (andhaloparaffin/phosphite if present) to yield isolated phosphono paraffin.

In at least one aspect, potassium iodide or potassium bromide isincluded in a reaction mixture of the present disclosure, instead of orin addition to, sodium iodide.

EXAMPLE 1

Scheme 2 illustrates reaction of 2,5,6,11,14-pentachloropentadecane(Cereclor AS45) with tributyl phosphite and sodium iodide.

Cereclor AS45 (Orica, now known as IXOM; 15.39 g) was dissolved intributyl phosphite (Acros, 150.19 g). Sodium iodide (Riedel-de Haen,29.98 g) was then added to form a reaction mixture. The reaction mixturewas stirred, brought under a nitrogen atmosphere, and heated toapproximately 160° C. At this point an exothermic reaction began and thetemperature increased to approximately 245° C. over a timespan of about30 minutes. The mixture was then slowly cooled over a time span of anadditional 30 minutes. Once at room temperature deionized water (100 ml)was added to the reaction product to form a biphasic mixture. Themixture was vigorously stirred, and then the water and organic phaseswere allowed to separate. The organic phase was drained from the aqueousphase and then distilled under vacuum to remove residual water andunreacted tributyl phosphite and Cereclor AS45. Distillation wasachieved at 153° C. at 0.618 mbar. The final mass of reaction productwas 26.98 g (58% yield).

The starting material and product had the following physicalcharacteristics:

Cereclor AS45 Product Physical appearance Viscous yellow- Yellow oilbrown oil Melting Point (° C.) −55 −73 Flash Point (° C.) 185 195 FirePoint (° C.) >250 245 Density (g cm⁻³) 1.16 1.023 ¹H NMR 3 broad complex4 sharp multiplets multiplets

FIG. 1 is an ¹H NMR spectrum (CDCl₃ solvent) of Cereclor AS45 startingmaterial. As shown in FIG. 1, the NMR spectrum contains multipletsbetween about 0.7 ppm and about 2.5 ppm and between about 3.5 ppm andabout 4.5 ppm. FIG. 2 is an ¹H NMR spectrum (CDCl₃ solvent) of thereaction product of Example 1. The reaction product has the structure(75):

As shown in FIG. 2, the NMR spectrum contains a multiplet between about0.75 ppm and about 0.9 ppm, a multiplet between about 1.3 ppm and about1.4 ppm, a multiplet between about 1.5 ppm and about 1.8 ppm, and amultiplet between about 3.9 ppm and about 4 ppm.

COMPARATIVE EXAMPLES

Comparative reactions were performed using other salts instead of sodiumiodide, as shown in Scheme 4.

When sodium bromide is mixed with Cereclor AS45 and tributyl phosphiteand heated, a phosphono paraffin is not formed.

Furthermore, mixing iodine (I₂) with Cereclor AS45 and tributylphosphite and heating the reaction mixture does not form a phosphonoparaffin at least for the reason that the boiling point of iodine islower than a reaction temperature of 160° C.

Lastly, when 20 mol % ZnBr₂ is mixed with Cereclor AS45 and triethylphosphite and heated, the mass of material remaining after removal oftriethyl phosphite by distillation indicates about 30% conversion ofCereclor AS45 into a reaction product having a phosphono paraffin, andthe ¹H NMR spectrum of the product is consistent with the mass ofmaterial determination. Furthermore, the expected zinc salts do notprecipitate from the reaction product, which should be removed for thephosphono paraffin to be used as a hydraulic fluid. In comparison,sodium salts, such as NaCl, formed during methods of the presentdisclosure do precipitate from the phosphono paraffin reaction product.Furthermore, ZnBr₂ is significantly more expensive than Nal, hinderingthe industrial applicability of ZnBr₂ as a reagent for large scalechemical reactions.

Formation of haloparaffins for subsequent phosphono paraffin formation:Haloparaffins can be formed by mixing C₁₋₂₀ alkanes with elementalhalogen (e.g., F₂, Cl₂, I₂, Br₂) to form a reaction mixture. Thereaction mixture is then exposed to ultraviolet (UV) light and/or aradical initiator to form a haloparaffin. Radical initiators includeperoxides, such as hydrogen peroxide.

As an example, in a nitrogen atmosphere, dodecane was mixed with 5 molarequivalents of Br₂ to form a reaction mixture. The reaction mixtureexposed to UV light to yield a reaction product having bromoparaffins.The reaction product was exposed to ambient atmosphere, quenched withwater and an organic solvent (hexane) was added to form a biphasicmixture having an aqueous phase and an organic (hexane) phase. Thebiphasic mixture was shaken and then allowed to settle. The organicphase of the biphasic mixture was drained. Hexane, residual water, anddodecane starting material were distilled from the organic phase toprovide bromoparaffin product (12% yield).

Hydraulic Fluids

Phosphono paraffins of the present disclosure can be used as hydraulicfluids. Phosphono paraffins of the present disclosure have viscosities,fire points, flash points, melting points, and biodegradabilityfavorable for use as hydraulic fluids. For example, fluoroparaffins areresistant to biological degradation, unlike phosphono paraffins of thepresent disclosure.

Phosphono paraffins may be used alone as a hydraulic fluid or mixed withother components to form a hydraulic fluid composition. Other componentsinclude water, a lower molecular weight phosphonates (such as tetrabutylpropyl bisphosphonate or tributyl phosphate), an antioxidant, a mineraloil, a vegetable oil (such as soybean, rapeseed, Canola, or sunflower),a glycol (such as propylene glycol), an ester, a silicone oil, analkanol (such as butanol), an alkylated aromatic hydrocarbon, apolyalphaolefin (such as polyisobutene), a corrosion inhibitor, andmixtures thereof.

Ester includes organophosphate esters, phthalates, adipates, phosphoricacid esters, and fatty acid esters. Antioxidant includes di-tertiarybutyl phenyl phosphite, octylated phenyl-alpha-naphthylamine,octylated/butylated diphenylamine, phenolics, and thioethers.

As used herein, wt % means weight percent and is based on the totalweight of the composition. In at least one aspect, a hydraulic fluidcomposition includes from about 1 to about 99 wt % phosphono paraffin,such as from about 10 to about 80 wt %, such as from about 20 to about70 wt %, such as from about 40 wt % to about 60 wt %. In at least oneaspect, a hydraulic fluid composition includes from about 1 to about 99wt % of other component(s), such as from about 10 to about 80 wt %, suchas from about 20 to about 70 wt %, such as from about 40 wt % to about60 wt %.

Hydraulic Fluid Composition Example 1

Phosphono paraffin (50-60 w/v %, such as 58 w/v %), dibutyl phenylphosphate (20-30 w/v %), butyl diphenyl phosphate (5-10 w/v %), anepoxide modifier (such as 2-ethylhexyl 7-oxabicyclo[4.1.0]heptane-3-Carboxylate <10 w/v %), and tri-cresyl phosphate (1-5 w/v %).

Hydraulic Fluid Composition Example 2

-   -   (1) phosphono paraffin from about 10 to about 80 wt %. In at        least one aspect, phosphono paraffin is present from about 20 to        about 70 wt %, such as from about 30 to 60 wt %.    -   (2) alkyl phosphonate from about 10 to about 20 wt %. In at        least one aspect, alkyl phosphonate is present from about 5 to        about 15 wt %.    -   (3) Skydrol additives <10 wt %.

Alkyl phosphonates include a monophosphonate compound represented byFormula 117:

wherein each of R¹⁷, R¹⁸, and R¹⁹ are independently C₁₋₂₀alkyl, aryl orC₁₋₂₀alkylaryl. Aryl includes monocyclic or bicyclic aryl. Aryl may bephenyl. C1-10alkylaryl includes C1-10alkylphenyl, such as benzyl.Monophosphonates include diethylbenzylphosphonate,dibutylhexanephosponate or dibutyloctanephosphonate

Hydraulic Fluid Composition Example 3

-   -   (1) siloxanes from about 20 to about 70 wt %. In at least one        aspect, siloxanes are present from about 20 to about 60 wt %,        such as from about 30 to about 50 wt %.    -   (2) phosphono paraffin from about 20 to about 60 wt %. In at        least one aspect, phosphono paraffin is present from about 30 to        about 50 wt %.

Siloxanes include polysiloxanes compound can be described according tothe following chemical structure Formula 118:

wherein y is an integer selected from 1 to 40: each of R¹, R², R³, andR⁴ is independently C₁₋₁₀alkyl, aryl or C₁₋₁₀alkylaryl; and R⁵ and R⁶are independently C₁₋₁₀alkyl, aryl or C₁₋₁₀alkylaryl.Polysiloxanes include:

Chemical Structure Substituents

R¹ and R² are phenethyl R³, R⁴, R⁵ and R⁶ are methyl y is 7

R¹ and R² are phenethyl R³ and R⁴ are methyl Each R⁵ and R⁶ is methyl orphenethyl y is 11

R¹ and R² are phenethyl R³ and R⁴ are methyl Each R⁵ and R⁶ is methyl orphenyl y is 11

R¹ and R² are phenethyl R³ and R⁴ are methyl Each R⁵ and R⁶ is methyl orphenethyl y is 11

R¹ and R² are phenethyl R³ and R⁴ are methyl Each R⁵ and R⁶ is methyl orphenyl y is 11or mixtures thereof.

Other uses of phosphono paraffins of the present disclosure include useas lubricants or as a solvent for extraction/purification of rare earthand actinide metals from ore.

Overall, methods of the present disclosure include synthesizingphosphono paraffins using sodium iodide to provide novel phosphonoparaffins having fire-resistance and biodegradability for use as ahydraulic fluid.

Definitions

The term “alkyl” includes a substituted or unsubstituted, linear orbranched acyclic alkyl radical containing from 1 to about 20 carbonatoms. In at least one aspect, alkyl is a C₁₋₁₀alkyl, C₁₋₇alkyl orC₁₋₅alkyl. Examples of alkyl include, but are not limited to, methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, andstructural isomers thereof.

The term “cycloalkyl” includes a substituted or unsubstituted, cyclicalkyl radical containing from 1 to about 20 carbon atoms.

The term “aryl” refers to any monocyclic, bicyclic or tricyclic carbonring of up to 6 atoms in each ring, wherein at least one ring isaromatic, or an aromatic ring system of 5 to 14 carbons atoms whichincludes a carbocyclic aromatic group fused with a 5- or 6-memberedcycloalkyl group. Examples of aryl groups include, but are not limitedto, phenyl, naphthyl, anthracenyl, or pyrenyl.

The term “alkoxy” is RO— wherein R is alkyl as defined herein.Non-limiting examples of alkoxy groups include methoxy, ethoxy andpropoxy. The terms alkyloxy, alkoxyl, and alkoxy may be usedinterchangeably. Examples of alkoxy include, but are not limited to,methoxyl, ethoxyl, propoxyl, butoxyl, pentoxyl, hexyloxyl, heptyloxyl,octyloxyl, nonyloxyl, decyloxyl, and structural isomers thereof.

The term “phosphono paraffin” includes a linear or branched alkanehaving one or more phosphono substituents.

The term “haloparaffin” includes a linear or branched alkane having oneor more halogen substituents. Halogen includes fluorine, chlorine,bromine, and iodine. Haloparaffin includes chloroparaffins,bromoparaffins, and iodoparaffins,

The term “phosphite” includes a trivalent phosphorous atom having threealkoxy substituents.

The term “primary halogen” includes a halogen atom bonded to a carbonatom that is bonded to two hydrogen atoms and one carbon atom, as shownhere:

The term “secondary halogen” includes a halogen atom bonded to a carbonthat is bonded to one hydrogen atom and two carbon atoms, as shown here:

The term “tertiary halogen” includes a halogen atom bonded to a carbonthat is bonded to zero hydrogen atoms and three carbon atoms, as shownhere:

Compounds of the present disclosure include tautomeric, geometric orstereoisomeric forms of the compounds. Ester, oxime, onium, hydrate,solvate and N-oxide forms of a compound are also embraced by the presentdisclosure. The present disclosure considers all such compounds,including cis- and trans-geometric isomers (Z- and E-geometric isomers),R— and S-enantiomers, diastereomers, d-isomers, I-isomers, atropisomers,epimers, conformers, rotamers, mixtures of isomers and racemates thereofare embraced by the present disclosure.

The descriptions of the various aspects of the present disclosure havebeen presented for purposes of illustration, but are not intended to beexhaustive or limited to the aspects disclosed, Many modifications andvariations will be apparent to those of ordinary skill in the artwithout departing from the scope and spirit of the described aspects.The terminology used herein was chosen to best explain the principles ofthe aspects, the practical application or technical improvement overtechnologies found in the marketplace, or to enable others of ordinaryskill in the art to understand the aspects disclosed herein. While theforegoing is directed to aspects of the present disclosure, other andfurther aspects of the present disclosure may be devised withoutdeparting from the basic scope thereof.

1.-12. (canceled)
 13. A phosphono paraffin represented by formula (I):

wherein: each instance of R¹ is independently —H or

each instance of R² and R³ is independently C₁₋₂₀ alkyl, cycloalkyl ofC₂₀ or less, or aryl; n is an integer between 4 and 22; and the numberof instances where R¹ is

of formula (I) is between about 2 and about
 8. 14. The method of claim13, wherein each of R² and R³ is independently C₁₋₅ alkyl or cycloalkylof C₆ or less.
 15. The phosphono paraffin of claim 13, wherein thenumber of instances where R¹ is

of formula (I) is between about 3 and about
 6. 16. The phosphonoparaffin of claim 13, wherein n is an integer between about 10 and about16.
 17. The phosphono paraffin of claim 13, wherein each of R² and R³ isindependently linear C₁₋₂₀ alkyl.
 18. The method of claim 17, whereineach of R² and R³ is independently C₁₋₅ alkyl or cycloalkyl of C₆ orless.
 19. The phosphono paraffin of claim 13, wherein each of R² and R³are the same.
 20. The phosphono paraffin of claim 13, wherein thephosphono paraffin has a fire point greater than about 200° C.
 21. Thephosphono paraffin of claim 20, wherein the phosphono paraffin has aflash point of greater than about 150° C.
 22. The phosphono paraffin ofclaim 21, wherein the phosphono paraffin has a melting point of lessthan about −40° C.
 23. The phosphono paraffin of claim 13, wherein thephosphono paraffin comprises:

wherein each of R¹ and R² is independently C₁₋₂₀ alkyl, cycloalkyl ofC₂₀ or less, or aryl.
 24. The phosphono paraffin of claim 23, whereineach of R¹ and R² are independently linear C₁₋₂₀ alkyl.
 25. The methodof claim 24, wherein each of R¹ and R² is independently C₁₋₅ alkyl orcycloalkyl of C₆ or less.
 26. The phosphono paraffin of claim 23,wherein each of R¹ and R² are the same.
 27. The phosphono paraffin ofclaim 23, wherein each of R¹ and R² are independently isopropyl, butyl,or phenyl.
 28. The phosphono paraffin of claim 13, wherein the phosphonoparaffin comprises:


29. The phosphono paraffin of claim 13, wherein the phosphono paraffincomprises:

and mixtures thereof.
 30. The phosphono paraffin of claim 13, whereinthe phosphono paraffin comprises:

and mixtures thereof.
 31. The phosphono paraffin of claim 13, whereinthe phosphono paraffin comprises:

and mixtures thereof.
 32. A hydraulic fluid comprising: the phosphonoparaffin of claim 13; and one or more components comprising water, alower molecular weight phosphonate, an antioxidant, a mineral oil, avegetable oil, an ester, a polyalphaolefin, a silicone oil, an alkanol,an alkylated aromatic hydrocarbon, a corrosion inhibitor, or mixturesthereof.
 33. The phosphono paraffin of claim 13, wherein each instanceof R² and R³ is independently C₁₋₂₀ alkyl or aryl.
 34. The phosphonoparaffin of claim 33, wherein the number of instances where R¹ is

of formula (I) is between about 3 and about
 6. 35. The phosphonoparaffin of claim 34, wherein each of R² and R³ is independently linearC₁₋₂₀ alkyl.
 36. The phosphono paraffin of claim 33, wherein n is aninteger between about 10 and about
 16. 37. The phosphono paraffin ofclaim 36, wherein each of R² and R³ is independently C₁₋₅ alkyl.
 38. Thephosphono paraffin of claim 37, wherein each of R² and R³ are the same.39. The phosphono paraffin of claim 33, wherein the phosphono paraffinhas a fire point greater than about 200° C.
 40. The phosphono paraffinof claim 39, wherein the phosphono paraffin has a flash point of greaterthan about 150° C.
 41. The phosphono paraffin of claim 40, wherein thephosphono paraffin has a melting point of less than about −40° C. 42.The phosphono paraffin of claim 33, wherein each instance of R² and R³is aryl.
 43. A hydraulic fluid comprising: the phosphono paraffin ofclaim 33; and one or more components comprising water, a lower molecularweight phosphonate, an antioxidant, a mineral oil, a vegetable oil, anester, a polyalphaolefin, a silicone oil, an alkanol, an alkylatedaromatic hydrocarbon, a corrosion inhibitor, or mixtures thereof.